Surface-active organoboron compounds

ABSTRACT

Organoboron compound having a structure exhibiting a hydrophilic group skeleton including a semipolar bond under normal conditions and a complex ion group skeleton in a basic medium or solution; the process for production of this compound; and its applications as an emulsifier and anti-static agent for plastics and as a heat stabilizer for plastics.

United States Patent Hamanaka et a].

SURFACE-ACTIVE ORGANOBORON COMPOUNDS Inventors: Hiroyoshi Hamanaka, Tokyo;

Yasuhisa Okazaki, lchikawa; Hiroshi Yoshijima, Chiba, all of Japan Assignee: Toho Chemical Industry Co., Ltd.,

Tokyo, Japan Filed: Nov. 30, 1971 Appl. No.: 203,464

Foreign Application Priority Data Dec. 3, 1970 Japan 45-106282 US. Cl 260/4l0.7, 252/356, 260/4585,

260/895 A, 260/3458, 260/410.6, 260/486 R, 260/928 R, 424/219 Int. Cl. C07d 107/02, C08k 1/60, B01f 17/34 Field of Search 260/4106, 410.7, 345.8, 260/462 Primary Examiner-Elbert L. Roberts Assistant Examiner-Diana G. Rivers Attorney, Agent, or Firm.loseph F. Brisbois 7 ABSTRACT Organoboron compound having a structure exhibiting a hydrophilic group skeleton including a semipolar bond under normal conditions and a complex ion group skeleton in a basic medium or solution; the process for production of this compound; and its applications as an emulsifier and anti-static agent for plastics and as a heat stabilizer for plastics.

17 Claims, No Drawings SURFACE-ACTIVE ORGANOBORON COMPOUNDS SUMMARY OF THE INVENTION The present invention relates to a new surface active organoboron compound, a process for its production, and applications of said compound. More specifically, it relates to a new surface-active organoboron compound having in its molecules at least one bond of the following type:

connecting a carboxylic acid ester radical and a polyoxyethylene radical, which can be expressed by the following general formula:

but when l=O and all of X, X, Y, Y are monovalent radicals, this formula will become as follows:

Z is H or H(OCl-l CH -),--or RCO(OCH C- H ),,-(R is an alkyl having 7 to 31 carbon atoms; and

O I+f 40) which definition applies to Z whenever hereinafter used in this specification, unless another definition is specifically indicated.

and least one of X, X, Y, Y is which group contains at least one Q OZ radical, where Z is RCO(OCH Cl-l but when l=0, X, Y are monovalent radicals and X, Y are divalent radicals, connected by an X-Y'forming-Mradical, this formula will become:

in which n 0,1,2 or 3; M is in which Z is as above defined;

in which Z is as above defined; and at least one of X, Y, M is an 0 Z 0 Z n 0 Z CHzOZ CHZO CH CH- group CHzOZ 0 Z which contains at least one OZ radical, where Z is RCO(OCH -CH but when [=0 and all of X, X, Y, Y are divalent radicals, with linkages X- -Y, -X-Y- forming -M and M' radicals, this formula will become:

l CHzOZ Z radicals, in which Z is as hereinbefore defined, and at least one of M, M is or CHzO (IE-[CH- H2OZ 0 Z which contains at least one OZ radical, where Z is RCO-(OCH CH but when i=1; X, X, Y, Y" are monovalent radicals and X=, Y are divalent radicals, with a linkage of YX"- forming W radical this formula will become:

(iv xi-cl-ro OHC-X,

Pro fi o l l w X A l: 5

HO OH i Y.- HO :r'ron Y,

10 where W, W are oz n radicals, in which n =0,l or 2, and Z is as hereinbefore defined. X,, X Y Y," are H or Hz(|]((|3H- oz oz 11,

radicals, in which n, 0 or 1, and Z is as hereinbefore defined; and at least one of W, W, X,, X,, Y Y," is 3O ':rr l radical or H2c JH oz n oz oz n,

at least one OZ radical, where Z is RCO- (OCH CH but when I 1 and all of X, X, X", Y, Y, Y are monovalent radicals, this formula will become:

CHO OHCX (v) X cHo fi oH Y W (3110 OHCX YLHO/III \OH Y 5+ where W is AZ n,

l in which n 0, l or 2 and Z is as hereinbefore defined;

X, Y are H or l mc- 3n oz oz n,

in which n =0, or 1, and Z is as hereinbefore defined; X, X, Y, Y are H, CH C H or in which n 0, l, 2 or 3 and Z is as hereinbefore defined; and at least one of W, X, X, X", Y, Y, Y is oz oz cals, with a linkage of XY forming M radical, this formula will become:

CH an radical, in which n,= 0, l or 2; and Z is as hereinbefore defined; X, Y are H or radicals, in which n O or 1; and Z is as hereinbefore defined; X, Y are H, CH C H or radicals, in which n 0, 1, 2 or 3; and Z is as hereinbefore defined; M is cH0Hzo 011-,

0 Z HzQZ in which Z is as hereinbefore defined;

OHzOCHCH,

radical, in which Z is as hereinbefore defined; and at least one of W, X, X, Y, Y, M is which contains at least one OZ radical, where Z is RCO (OCH CH but when l= 1', X, Y are monovalent radicals and X, X", Y, Y" are divalent radicals, with linkages of XY, X"Y forming M-radical and -M' radical, this formula will become:

-CI-I- a l,

in which n,==0, 1 or 2; and Z is as hereinbefore defined;

X, Yare Hor l oz oz n,

in which n O or 1 and Z is as hereinbefore defined; M, M are in which Z is as hereinbefore defined;

radicals. in which Z is as hereinbefore defined; and at least of W, X, Y, M, M' is which contains at least one OZ radical, where Z is RCO-(OCH CH This new organoboron compound is obtained by first reacting one mol of boric acid or a triester borate of a monohydric lower alcohol with from one to two mols of at least one kind of polyhydric alcohol having vicinal hydroxyl radicals (hereinafter to be called the specified polyhydric alcohol) in such a manner that the total sum of hydroxyl radicals in the molecule of the specified polyhydric alcohol is 5 or more for each boron atom in the molecule of boric acid or each boron atom in the molecule of the triester borate of a lower alcohol, thereby producing a triester borate of the specified polyhydric alcohol with at least two hydroxyl radicals remaining in the molecule; then adding 140 mols of ethylene oxide to one mol of the resulting triester borate of the specified polyhydric alcohol with non-protonic Lewis acid in such a manner that the average degree of polymerization of the polyoxyethylene radical in the molecule of the end product amounts to 1-40; and thereafter reacting said triester borate of the specified polyhydric alcohol with a carboxylic acid having alkyl radicals with 7 to 31 carbon atoms (hereinafter to be called the specified carboxylic acid) or a lower alcohol ester of the specified carboxylic acid, or an acylhalide of the specified carboxylic acid, with the alcohol group having, in either case, at least one derived terminal hydroxylic radical.

The surface-active orgaonboron compound of this invention excels as a hydrophilic surface-active agent and is useful as an emulsifier or dispersing agent for various materials; as an anti-static agent for synthetic resins and as an anti-fogging agent. In terms of basic properties such as surface tension decreasing ability and wetting power, the invented compound surpasses the conventional ester type surface-active agents, i.e., polyoxyethylene sorbitan fatty esters (Tween type) or fatty acid esters of polyethyleneglycol. Moreover the heat stability of the compound itself is far better.

In describing the present invention, a particularly detailed account of the starting materials and the reacting conditions will be given.

First, suitable polyhydric alcohols having vicinal hydroxylic radicals to be reacted with boric acid or a triester borate of a lower alcohol to-produce a triester borate of polyhydric alcohol which is to constitute a hydrophilic group skeleton, include the following substances: ethyleneglycol, propyleneglycol, butyleneglycol, glycerine, sorbitan, sorbitol, manitol, etc. Meanwhile, suitable triester borates of a lower alcohol include: trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, etc. Here, the esterification reaction using boric acid and a polyhydric alcohol can be easily promoted by heating and dehydrating under reduced or normal pressure at 300C, or preferably at l-2 10C, while the ester interchange reaction using a triester borate of lower alcohol and a polyhydric alcohol can be easily promoted by removing the side product, i.e., lower alcohol under reduced or normal pressure at 50250C or preferably at lO()-l80C. In this case the restrictive conditions for charging the materials and assuring the abovementioned structural dislocation of the resulting hydrophilic group skeleton are that two mols of at least one kind of polyhydric alcohols be used per mol of boric acid or a triester borate of lower alcohol; and that the proportions of charged materials be so selected that the total number of hydroxylic radicals, including those which become polyoxyethylene radicals in the next stage of production is 5 or more per boron atom. For this reason, the dihydric alcohols such as ethyleneglycol, propyleneglycol cannot be used alone; they must be combined in use with a more than dihydric alcohol.

In this reaction, usually no esterfication catalyst is needed; an inert gas such as nitrogen or carbon dioxide gas is introduced for the purpose of facilitating completion of the reaction. Azeotropic dehydration may be carried out by means of a solvent such as xylene, toluton. The Lewis acid catalysts available for this purpose include: boron trifluoride ethyletherate BF3.O(C H tin chloride (IV) SnCl antimony chloride (V) SbCl titanium chloride (IV) TiCl iron chloride (Ill) FeCl zinc chloride (IV) ZnCl phosphorus pentoxide P aluminium chloride (1) AlCl etc.; 0.00l-5% or preferably O.3l% of such catalysts should be used for the triester borate of the specified polyhydric alcohol obtained in the preceding stage and then the reaction will proceed with the reaction temperature 50250C, or preferably 70l 50C, and a reaction pressure of atmospheric pressure to Kglcm or preferably 1-5 Kg/cm The necessary condition which makes it possible for the surface-active organoboron compound of this invention obtained through the next carboxylic acid esterification reaction to exhibit excellent performance as a surface active agent is that in this stage an ethylene oxide adduct of l-4O in average degree of polymerization be produced.

The present inventors tried to synthesize a propylene oxide adduct in this stage and derive therefrom a surface-active organoboron compound in the same manner as this invention, but the product thus obtained turned out to be inferior to the product derived from the ethylene oxide adduct. On the other hand, we investigated similar products containing a mixed chain of I ethylene oxide and propylene oxide, but in this case too the results of testing them provied unimpressive.

Next, turning to the problem of carboxylic acid esterification for deriving the end product of this invention, i.e., the surface-active organoboron compound, the carboxylic acids suitable as the surface-active agent are carboxylic acids containing saturated or unsaturated alkyl radicals having 7 to 31 carbon atoms or halogentated or hydroxylated alkyl radicals. More specifically, the following natural or synthetic substances can be mentioned: caprylic acid, lauric acid, palmitic acid, stearic acid, branched stearic acid, hydroxystearic acid, linoleic acid, ricinoleic acid, a bromopalmitic acid, a chlorostearic acid, oleic acid, behenic acid, lignoceric acid, cerotic acid. Now, the direct esterification between these carboxylic acids and the product obtained in the preceding stage can be easily promoted by heating and dehydration under reduced or normal pressure at 70 250C or preferably at 180 230c. Turning now to the ester interchange reaction with use of methylalcohol ester: a methyl alcohol ester of the above-mentioned carboxylic acids can be made easily under reduced or normal pressure at 50200C or preferably at 80l50C.

On the other hand, in the esterification by dehydrohalogenation with use of an acyl halide of carboxylic acid, a carboxylic acid ester can be easily produced under reduced or normal pressure at 30-l50C or preferably at 6080C. Moreover, this carboxylic acid esterification is characterized by the reaction completing itself without using any special esterification catalyst such as an alkali, alkaline metal or acid, no matter what method is adopted. Of course, the said carboxylic acid estrification is also completed with the use of such catalysts. Also in this reaction, the smooth progress of reaction will be facilitated by the introduction of an inert gas such as nitrogen or carbon dioxide gas or by.

the use of an azeotropic solvent or a dilution solvent for the purpose of dehydration.

By tracking the structure in the compound thus obtained through IR spectral analysis and NMR spectral analysis, the present inventors have been able to confirm that this organoboron compound, just like the organoboron compound covered by U.S. Pat. application Ser. No. 882,342, filed Dec. 4, 1969, now U.S. Pat. No. 3,772,357, is characterized by a structural dislocation depending on the ambient atmosphere. Specifically, under normal conditions this compound possesses a hydrophilic group skeleton including a semi-polar bond as follows:

In a basic medium or solution however, this structure is transformed to that of a complex ion group as follows:

This structural dislocation exhibited by the invented compound is an action resulting from the excessive OH radicals in the end product existing in the range of being able to form a coodinate bond with boron atoms of triborate structure according to the selection of above-mentioned appropriate proportions of charged materials with a polyhydric alcohol having vicinal hydroxylic radicals as the starting material.

To cite a relevant example of structural analysis, the following observations are made in the IR spectral analysis of the organoboron compound according to this invention: Whereas in normal condition the characteristic absorption band supposed to be due to (out-of-plane deformation vibration of Ql-l) is conspicuous at 830 cm, the structure of this compound is completely changed to an ion structure when this compound is neutralized with alkali in a nucleo-philic field and the above-mentioned characteristic absorption band appearing at 830 cm vanishes. This is proof of the above-mentioned structural dislocation. With the known triester borates, the abovementioned absorp tion band is not recognized.

As the known organoboron compounds containing polyoxyethylene radicals may be mentioned many substances with a boric acid ester as the terminal hydroxylic radical in an alcohol-ethylene oxide adduct having the general formula (R[O-(CH ,,-O) B as illustrated by British Pat. Specification No. 1214171. In addition, the Japanese Pat. Publication Sho. 4224043 and U.S. Pat. No. 3,373,170 disclose a structure of surface-active agent with a boric acid ester in place of polyoxyethylene sorbitan monoalkylate.

The surface-active organoboron compound of this invention is remarkable not only in that it is structurally different from the compounds mentioned above, but also in that it is produced by a new, unique process. To go into details about this, according to this invention in the first stage of production the boric acid triesterification of a polyhydric alcohol having vicinal hydroxylic radicals takes place under the above-mentioned materials charging conditions to produce a compound in whose molecules coexist radicals and excessive OH radicals dition of ethylene oxide does not cease at the extent of several mols as happens with the ordinary reaction under use of an acidic catalyst, but can produce a highmol addition polymer.

Further they have discovered the singular fact that the ethylene oxide addition reaction will take place only in the presence of a Lewis acid catalyst and this is recognized as a remarkably different reaction from the ethylene oxide addition to the alcoholic OH radicals in conventional processes for the production of surfaceactive agents. Specifically, the experimental results show that the addition reaction of this invention will not take place at all when a conventional alkali catalyst, alkaline metal catalyst, or alcoholate catalyst is used. And even with no use of any catalyst, or with the use of a proton acid catalyst no addition of ethylene oxide will occur.

The following are investigative data on the weight in crease of the formed product and the volume of byproducts when 88g(2.0 mol) of ethylene oxide was added at a flow rate of 0.5 l/min under normal pressure to 19.2 g(0.1 mol) of bis-(glyceryl-a,B-) boronium hydride, i.e., one of the intermediate products in this invention in presence of different catalysts.

CHO OHC In the second stage, the ethylene oxide addition takes I 20 i catalyst place using a Lewis acid catalyst and as a result the ad- +H dition of ethylene oxide is made only in the remaining crnon crnort Addition of ethylene oxide to bis(glyceryl)u,fi-) horonium hydride in presence of different catalyst Volume Volume Ratio of of in- Weight of catalyst troduced [11- by- Matcrials to Reaction ethylene creased product Catalyst charged materials temperature oxide No catalyst 19.2 g w 140C 88g (071) (0%) KOH do, 0.2'71 l4() do. (0%) NatMetal) do. 0.] l3tl do. (UV! OI/I) NuO CH do. ().2 I40 tlt). ((1%) tract- BF H do. 0.2 l lll (lu. 701117957! J 151M407: J do. do. ().2 I30 do, llllgt) l .()'/r) 4.7g(5.3'/r; S,,(l, do. 0.3 so a. ()Sg(73.)'/r) l.5g( 1.7%) S,,Cl do. 0.5 X0 do. SXgUilxW/r) lfigt l,7'//) H SO do. 0,3 lll) do. ((l/r) trace HNQ. do. 0.2 I34) do. (W/1) trace portion of the excessive OH radicals without causing any change in the OH radicals forming a semi-polar bond in the above-mentioned t'lto' radicals In connection with this addition reaction, the present inventors have discovered a valuable fact in that the adradicals, through a potentiometric titration conducted using a methanol caustic potash in a solvent of methanol-acetone (1:1), whereby the product of the second stage was neutralized with the consumption of the lg equivalent of caustic potash as calculated from the structural formula.

Next, turning to the carboxylic acid esteriflcatioin with some of the OH radicals, to be carried in the third stage for the purpose of introducing hydrophobic radicals, similarly the retention of radicals has been verified through a potentiometric titration conducted under the same conditions as above, whereby approximately lg equivalent of KOH was also consumed. Thus it has been revealed that carboxylic acids react selectively with the terminal hydroxylic radicals in polyoxyethylene radicals.

The following are specific examples illustrating the process of the present invention. Example 1 61.8 g (1 mol) of boric acid and 184.2 (2 moles) of glycerine were charged into a four necked flask equipped with a stirrer, a thermometer, a gas-introducting pipe, and a water measuring tube connected to a reflux condenser. Then, with nitrogen gas introduced, dehydration was carried out at 180-210C, taking 4 hours. As a result, with 54 g of water removed, a triester borate was obtained as a clear liquid. This liquid was subjected to neutralization titration with alcoholic caustic potash in a mixed 50:50 alcohol-ether solvent and its acid value was found to be 288 (theoretically 292). Then this liquidwas poured into a pressure autoclave, into which 0.95 g (0.5% based on starting material) or boron trifluoride etherate (35% ethylether solution) was added as a catalyst. Thereupon, under a pressure of 3-4 kg/cm and at 130C, 440 g mols) of ethylene oxide was added thereto, taking 2 hours; and as the result, a clear yellowish liquid was produced.

The total volume of the ethylene oxide adduct thus obtained was returned to the above-mentioned four necked distillation flask, to which 144.1 g (1 mol) of caprylic acid was added; and thereafter under introduction of nitrogen gas, dehydration was carried out at 180200C, taking 5 hours. After removal of 18 g water, a reddish brown oily substance resulted. Neutralization titration of this reaction product showed its acid value to be 68 (theoretically 74). When the IR absorption spectrum of this product showed that the C=O stretching vibration (1,710cm) due to the free carboxylic acid abated and only the C=O stretching vibration (1,740cm) corresponding to perfect conversion to ester linkage remained, the reaction was judged to have been completed.

(structural formula) CIIQO OIL-C Emission spectrum 2496.8A 2497.7A (B) IR absorption spectrum (measured) Example 2.

145.8 g (1 mol) of triethyl borate, 92.1 g (1 mol) of glycerine and 62.1 g (1 mol) of ethylene glycol were charged into the same apparatus as employed in Example 1. In a nitrogen gas stream, deethanolization was carried out at 130C, taking about 5 hours and this process yielded a clear liquid substance with an acid value of 340.5. After 1.5 g (about 1% based on starting material) of titanium tetrachloride was added thereto, 704 g (16 mols) of ethylene oxide was introduced at 90C, taking 5 hours, under a rather mild passage of nitrogen gas; after 30 minutes of aging thereafter, a yellowish liquid product was obtained. Then 214 g (1 mol) of methyl laurate was added to this reaction product and after about 5 hours of demethanolization at 180C, a yellowish oily substance with an acid value of 48 (theoretically 52) was produced.

(Structural formula) C1110 OH O l l CH0 5 oHro CH;O(CHzCHzO-)16.0 C(CH2)IOCH3 ('y-lauroylpolyoxyethylene Emission spectrum 2496.8A 2497.7A (B) IR absorption spectrum 1735cm (vC=O) l400cm-1480- (vB-O) cm 830cm (8B...HO

(measured) (theoretical) 0.98% 1.01%

13 Example 3.

187.8 g (1 mol) of triisopropyl borate, 92.1 g (1 mol) of glycerine and 76.1 g (1 mol) of propylene glycol were charged into the same apparatus as employed in Example 1. During the introduction of nitrogen gas, an ester interchange reaction was carried out at ll20C, taking 6 hours. After removal of nearly the specified amount of isopropyl alcohol, a yellowish liquid substance was produced. 0.5 g (about 0.3% based on starting material) of zinc (IV) chloride was added to this liquid and thereafter, 880 g (20 mols) of ethylene oxide was introduced at 120C. It took about 6 hours to complete the addition reaction, which yielded a yellowish liquid substance.

Next, after hours of reaction at 140C with 256 g (1 mol) of palmitic acid and 200 g of xylene as an azeotropic solvent, 18 g of water was removed. Under reduced pressure, the xylene was distilled off, leaving a yellowish paste with an acid value of 38.

(structural formula) mo-wmcmo-mo Gammon,

Emission spectrum 2496.8A 2497.7A (B) IR absorption spectrum Example 4.

618 g mols) of boric. acid and 1,842 g mols) of glycerine were charged into the same appartatus as employed in Example 1. During the introduction of nitrogen gas, dehydration was carried out at 200-2l0C, taking 6 hours. Removal of 535 g of water left a clear triester borate liquid with an acid value of 290 (theoretically 292). The total volume of this liquid was introduced into a pressure autoclave, into which 60 g (about 3% based on starting material) of boron triflfuoride etherate 35% ethyl ether solution) was added as a catalyst. Then under a pressure of 5 kg/cm at 130C, 10560 g(240 mols) of ethylene oxide was introduced, taking about 10 hours and as the result a yellowish clear liquid with an acid value of 43 (theoretically 45.1) was produced. Next, 1,248 g (1 mol) of this ethylene oxide adduct was introduced into a four-necked distillation flask equipped with a stirrer, a thermometer, adropping funnel and an adapter. After the addition of monochlorobenzene 500 g as a dilution solvent, 302.5 g (1 mol) of stearoyl chloride was introduced at 70C through the dropping funnel, taking about 2 hours. Then, with a gas-introducing pipe provided, hy-

(Structural formula) CHzO OlIzC glyceryl-a, B, polyoxyethylene glyceryl-a, fi-) boronium. hydride Emission spectrum 2496.8A 2497.7A (B) IR absorption spectrum l735cm (C=O) 1400-1480cm (8-0) (measured) (theoretical) 0.69% 0.11%

Example 5.

1,248 g 1 mol) of triester borate containing polyoxyethylene radicals, i.e., the intermediate product with an acid value of 43 as obtained in the first and second stages in Example 4, was introduced into a four-necked distillation flask equipped with a stirrer, a thermometer, a gas-introducing pipe and a water measuring tube linked to a reflux condenser. 284 g (1 mol) of branched stearic acid suitable for industrial use was added thereto. Then, in a nitrogen gas stream at 200-230C, 18 g of water wasremoved, taking 5 hours, a yellow clear oily substance with an acid value of 32 was produced. (Structual formula) (Structural formula) Emission spectrum 2496.8A 2497.7A (B) IR absorption spectrum 1740 cm" (vC=O) 4 .4Q.. m-

(measured) (theoretical) (Structural formula) ClIiO OHrC HO l OHC-CHiO( GH CH1O) .OGC H bis('y-stearoylpolyoxyethylene glyceryl-zx, fl-)boron1um hydride Emission spectrum 2496.8A 2497.7A (B) IR absorption spectrum (measured) (theoretical) ample 4, and 282 1 mol) of oleic acid were charged intothe same apparatus as used in Example 5. After 6 hours of dehydration at 230C in a nitrogen gas stream 18g of water was removed and an orange-yellow liquid (Structural formula) cmo 0112c Emission spectrum 2496.8A 2497.7A (B) IR absorption spectrum l745cm vc'=o) l4O()l48Ocm (IIBO) (measured) (theoretical) Example 8.

2,496 g (2 mols) of triester borate containing polyoxyethylene radicals, i.e., the intermediate product in Example 4, and 846 g (3 mols) of oleic acid were charged into the same apparatus used in Example 5. Taking 6 hours in a nitrogen gas stream at 240C, the specified extent of dehydration was nearly attained, leaving an orange-yellow liquid.

(Structural formula) a mixture 0! H10(cHlCHIO) .0 C(CHa)1 CH=CH(CH2)1CHJ m+n=24 bis(v-oleoylpolyoxyethylane 3 glycerylfl-) boronium hydride and CHZO 01120 l HO 2 OH CHiO-(CHzCHzO)mH Hz 0-(CHQCHZO )n-OC(CH1)7CH=CH(CH2)7CH3 .WBFBfZE .2

4O Emission spectrum 2496.8A 2497.7A (B) IR absorption spectrum 1745CITF' (VC=0) v 1400-1480cm (UBO) (measured) (theoretical) 0.62% 0.68%

Example 9.

1,248 g (1 mol) of triester borate having polyoxyethylene radicals, i.e., the intermediate product in Example 4, and 200.3 g (1 mol) of lauric acid were charged into the same apparatus as used in Example 5. Taking 6 hours in a nitrogen gas stream at 210C, 18 g of water was eliminated, leaving a light yellow liquid.

(structural formula) Emission spectrum Emission spectrum 2496.8A 2497.7A (B) 2496.8A 2497.7A (B) IR absorption spectrum IR absorption spectrum l735cm"(vC=O) l735cm (vC=O l400-l480cm (vB-O) l400-l480cm (VB-O) (measured) (theoretical) (measured) (theoretical) 0.75% 0.76% 10 0.57 0.61%

Example 10. Example l2 1,248 g of tflestef bOfale contalnmg p y xy- 1248 g 1 mol) of triester borate containing polyoxyethylene fadlcals, the lntefmedlate Product In ethylene radicals, i.e., the intermediate product in Example and 400-6 g mols) 0f t' 801d were ample 4, was introduced into afour necked distillation charged into the same apparatus as used in Example 5. fl k i d i h a stirrer, a thermometer, a d

Taking 6 i'lOUl'S in 8. nitrogen gas stream at220C, 36 ping funnel and an adapter, and at 70C 274,5 g (1 g of Water was eliminated yielding an Orange-yellow mol) of palmitoyl chloride was dropped therein, taking iq i about 2 hours. Then with the dropping funnel replaced by a gas-introducing pipe, taking about 3 hours in a nitrogen gas stream at 120C, hydrochloric acid was removed, and as the result a light yellow pasty substance (structural formula) was produced. (I l: O 01 {2C B I C II 0 l O1lCCIlz O (CIIgCIl O in. O C(C}{1 1QCII3 (structural formula) CI-IgO-(CH CHzO) n.OC(CH2)1uCHa CHQQ OHQC m+n=24 \E/ bis ('y-lauroylpolyoxyethylene glyceryl-a, 8-) boronium hydride H O /O H C--CII O(CI-I2CII;O) .11

(vpalmitoylpolyoxynl hyltu 1n Emission spectrum glycury|-a,b-. "p0lyoxyc:thyleue glyceryl-ix,B-)b0r0mum hydride 2496.8A 2497.7A (B) 40 IR absorption spectrum l735cm (1'C=O) l400l480cm" (VB-O) Emission spectrum B 2496.8A 2497.7A (B) i if gf gga IR absorption spectrum l735cm" (11C=()) Moo-148mm wB0) Example 1 l. 7 B

1,248 g (1 mol) of triester borate containing polyoxyethylene radicals, i.e., the intermediate product in Ex- (measured) 0.69% 0.73% ample 4, and 56.0 g (2 mols) of llnoleic acid were introduced into the same apparatus as used in Example 5. Spending about 8 hours in a nitrogen gas stream at Example 13 200220C, 35.5 g of water was removed, yielding a 164 g (1 mol) of crystalline sorbitan, 92.1 g 1 mol) yellow-brown oily substance. of glycerine and 164.8g (corresponding to 1 mol) of a (structural formula) cl-no 01120 1 (no it)IICCH;O(CH;CH O)m.0 C(CH;);CH=CHCH1CH=CII(CH),CHJ

bis (y-linoleoylpolyoxyethylene glyceryl-a, 6-) boronium hydride 19 20 63% methanolic solution of trimethyl borate were inwas added. Then, with the temperature raised to troduced into a four-neck distillation flask equipped 240C, 35 g of water was removed over a period of with a stirrer, a thermometer and a vacuum apparatus, about 8 hours, yielding a light yellow paste.

(Structural formula) ft CH0 OHQC l l CH3(CHr) CO-(OCH;ClIz)nOCHrCH no \OH cfi C H 0(CH1CH2O)l-O C(CHmOCl-l: l m l 11:25 H-(OCI-IrCHr-)mC and at 7580C, and 5-l0mmHg, demethanolization Emission p c was carried out for 6 hours to distill 155 g of methanol.

. 24 7. 0.25 g (about 0.11% based on starting material) of 2496 8A 9 7A (B) stannyl(lV)chloride was added to the light yellow vis- 1R absorption spectrum cous substance thus produced,-and after the tempera- ("(3:0) ture rose to 200C, 880 g (2O mols) of ethylene oxide l4oo i4socm (uB-O) was slowly introduced under normal pressure, taking about 10 hours, and this was followed by one hour of B aging. The result was a light yellow liquid with an acid (measured) (theoretical) value of 45. 0.50% 0.54%

Then, with the vacuum apparatus refitted, 298 g (1 mol) of methyl 12-hydroxystearate was added, and at l20-130C, 5l0mmHg. about g of methanol was Example 15 distilled away, taking 3 hours, yielding a brownish wax- Using the same equipment as used in Example 1, 260 like substance. g (corresponding to 1 mol) of a 70% aqueous solution V V (structural formula) V 7 CH2 o \CHO OHQC l l CHa(CH2)a-$H(CH2)ioCO-(OCHzCH2)n-OCI-Ii H /C1-IO l \OHI OH \CIJH cHr0- cHrcH2o- |H z Hz)m-O l+n1+n=20 Emissim' SPCtrum 40 of sorbitol, 180 g (2 mols) of 1,2-butylene glycol and 2063A 2497' (B) 123.7 g (2 mols) of boric acid were mixed together.

During the introduction of nitrogen gas the tempera- IR absorption Spectrum ture was raised to 210C, over about 6 hours, and 185 "400W, Mk0) g of water was thereby r emoved, leaving a slightly yel- 1400-1480errr' (vB-C) low VISCOUS substance with an acid value of 297. Then B 4 g (about 1% based on starting material) of antimony(V)chloride and 1320 g (30 mols) of ethylene (measured) (theoretical) oxide were introduced at 150C, taking about 16 hours,

068% 076% and yielding an orange-yellow oily substance.

Next, 467.5 g (1 mol) of fatty acid (major contents:

Example C 17.3%, C 35.1%, C 32.8%) obtained by the de- Using the Same equipment as used in Example 1, 164 composition of rice bran oil was added; and at 240C, g (1 mol) of manitan powder, 921 gm mol) of g1ycer the reaction was continued for 12 hours. After the inc and 2293 g (1 mol) of tributyl borate were mixed elimination of 17.5 g of water, a yellowish brown waxtogether. Debutanolization for ester interchange was like substance was Producedcarried out for 6 hours in a nitrogen gas stream at 200C, thereby yielding a colorless clear viscous sub stance having an acid value of 206 (theoretically 212). (structural fmmula) I 0x120 01120 This substance was placed in a pressure autoclave; L l

and using 0.5 g (0.2% based on starting material) of LCZHs aluminum (Ill) chloride as a catalyst, under a pressure I 6-8 kg/cm and at a temperature of 180-200C, 1100 Cmwmmcwwomcfir*0 CH i g (25 mols) of ethylene oxide was reacted therewith taking about 4 hours, and yielding a yellow clear liquid. 2

' B 1,360 g (1 mol) of the resulting ethylene oxide adduct was again introduced into the four-necked distilla- 1 tion flask, to which 681.2 g (2 mols) of behenic acid m n=30 6+ Emission spectrum 2496.8A 2497.7A (B) IR absorption spectrum 1735cm (vC#)) l400-l480cm- (uB-O) (measured) (theoretical) 0.98% 1.00%

Example 16.

Using the same equipment as used in Example 1, 61.8 g (1 mol) of boric acid and 184.2 g (2 mols) of glycerine were mixed together, and during the introduction of nitrogen gas, at 210C the reaction mixture was dehydrated for 5 hours. The elimination of 54 g of water yielded a colorless clear liquid of triester borate with an acid value of 290.

Next, 6 g (3% based on starting material) of boron trifluoride etherate ethylether solution) was added; and after heating up to 120C, with the introduction of 1,760 g mols) of ethylene oxide together with nitrogen gas, the addition reaction took 16 hours. This was followed by addition of 568 g (2 mols) of stearic acid and 8 hours of dehydration at 240C, during which 35.5 g of water was removed. The yield was a yellowish brown paste.

Emission spectrum 2496.8A 2497.7A (B) IR absorption spectrum (theoretical) 0.43%

(measured) 0.40%

Example 17.

Using the same equipment as used in Example 1, 61.8. g (1 mol) of boric acid and 184.2 g (2 mols) of glycerine were mixed together, and dehydrated during the introduction of nitrogen gas at 210C, taking 5 hours. The elimination of 54 g of water yielded a colorless clear liquid of triester borate having an acid value of Next, 3 g (1.5% based on starting material) of aluminum chloride was added; and after heating up to 100C, under normal pressure 88 g (2 mols) of ethylene oxide was slowly added.

Then, 400.6 g (2 mols) of lauric acid was poured in and in 6 hours at 200C, 36 g of water was eliminated 22 in a nitrogen gas stream, thereby yielding a light yellow paste with an acid value of 84 (theoretically 87) as the reaction product.

Using the same equipment as used in Example 1, 145.8 g (1 mol) of triethyl borate, 92.1 g (1 mol) of glycerine and 62.1 g (1 mol) of ethyleneglycol were mixed together, and deethanolized in a nitrogen gas stream at 130C for about 4 hours, thereby, yielding a colorless clear liquid with an acid value of 340.

Next, 1.5 g (about 1% based on starting material) of boron triflouride etherate (35% ethylether solution) was added; and at 100C, 220 g (5 mol) of ethylene oxide together with nitrogen gas was introduced, taking about 5 hours. Thirty minutes of aging thereafter completed the addition reaction.

This was followed by the charging of 256 g (1 mol) of palmitic acid; and after heating up to 230C, 18 g of water was removed as the byproduct, taking about 6 hours. Thus a light yellow paste was produced.

(Structural formula) Emission spectrum 2496.8A 2497.7A (B) IR absorption spectrum (measured) 1.70%

(theoretical) 1.74%

Further examples carried out by methods similar to Character of the final product.

B i 1 Method llt l lx. similar I absorption Theo- 32 to 14 Starting materials and final product spectrum Found retical CIIZOII CH2 ()CI'Iz C11'zCIIz,

OIIOII ITOIIC (I) BOCII3 HOCH IIOHC CHCI'IZOH, OCH CH (CH COOII CHOII CHOH CHOII GHzOH,

015 1,750 c637 0. 72 o. 72 crno one (V l W l f (5H0 E OHC CHCHz0(CHzCHzO-) OC(CHz)nCH3 H(0CH2CH;) 1-OCH MP1 0HO-(CHzCHzO-)i-H OHO-(CHzCHz-)r-OC (CH2)14CH CH2 LNG-1,480 cm.- CH0 CH0 0 (VB-O) l W I l CH O i/ OHC /CHCH (C 2CH20)mOC(CH2)14CH3 mi GHO-(OHzCHzO-) nOC(CH2)1lCH3 i+i+k+l+m+n=35 The products obtained according to the present ini vention, when used directly as non-ionic surface-active agents, or used after being rendered anionic by dislocation of the structure through addition of amine or alkali, or used in combination with other surface-active agents, exhibit excellent surface activity with unique features in various fields of application.

The following examples illustrate their performance, I

especially as an emulsifier or an anti-static agent for synthetic resins. 1. Examples of emulsification tests A. 16g of stearic acid, 10 g of propylene glycol, 2 g of Span 60 and 6 g of the reaction product of Example 4 were introduced into a 200 cc beaker. The whole thing was heated to melt at 65-70C; and after being evenly mixed, 66 g of warm water at a temperature of 60C was slowly added under agitation and then it was cooled. Th emulsified product thus obtained turned out to be a homogeneous, stable, creamy substance, thereby verifying the strong emulsifying power of the reaction product obtained in Example 4.

B. A comparison of washable cream emulsifying power under'slightly alkaline conditions was made between the reaction product of Example 2 and Tween 20.

Emulsion Formulations MOWIIILIILIIUJQ Total Emulsion FormulationsContinued Total 100 g After one-year long stability tests of the two creams compounded by the above-mentioned formulations under a constant temperature of 20C and a constant relative humidity of 65%, the cream compounded with the product according to Example 2 of the present invention (formulation I) remained stable for one year in the emulsified state, whereas the control cream emulsified by Tween 20 the fatty components became segregated in three months, thus verifying the excellent emulsifying power of the neutralizate of the product of Example 2 with triethanolamine.

C. The emulsification stability of a mixture of liquid paraffin and beeswax with sorbitan sesquioleate when prepared with the reaction product of Example 7 and with Tween 80 were compared. The formulations were as follows:

Emulsion formulations (Formulation 1) Liquid paraffin 25 Sorbitan sesquioleate 1.5

Reaction product of Example 7 3.5

Water Total Emulsion formulations Continued (Formulation 11) Emulsification stability observations were made of these four formulations for 10 days in a 40C constant temperature drying oven. On the second day, water separated out at the bottom of emulsions of formulations 11 and IV using Tween 80, while the emulsions of formulations I and 111 using the product of Example 7 according to the present invention remained stable with no water separated after 10 days.

D. The stability of methyl methacrylate monomer emulsification was compared between the following two formulations using respectively the reaction prod- .uct of Example 5 according to the present invention and Poly(24)oxyethylene sorbitan monoisostearate.

(Formulation I) MMA monomer 50 g Reaction product of Example 5 5 Water 125 Total 180 g (Formulation II) MMA monomer 50 g Poly(24)oxyethy1ene sorbitan 5 monoisostearate Water 125 Total 180 g The stability of the above two formulations was observed for one month under a constant temperature of 20C and a constant humidity of 65%. The results showed that in the emulsion using p0ly( 24 )oxyethylene sorbitan monoisostearate under formulation II separated and MMA monomer separated on the second day, but the emulsion using the reaction product of Example 5 according to the present invention remained stable enough even after a full month.

2. Examples of tests for anti-static effect A. Results of testing the effect of the reaction product of Example 8 as an anti-static agent for methyl methacrylate resin are cited here. As the control substance, a surfactant of phosphate type with the following structural fonnula was adopted:

(Formulations) 1 MMA monomer parts Reaction product of Example 8 1,2,3 or 4 parts 11 MMA monomer 100 parts Control with the above structure Manufacturing process: Monomer-casting method Polymerization Aging 1,2,3 or 4 parts 90C, 10 hours C, 2 hours Anti-static effect:

1. At 20C, 65% RH, the surface resistivity was measured with the following results:

Amount of addition Surface resistivity Blank 3.61XIO" (1 Product of Example 8 1 part l.62 l0 do. 2 part 9.67 10 do. 3 part 892x10" do. 4 part 1.08XIO" Control substance 1 part 3.61X10 do. 2 part 430x10" do. 3 part 1.85Xl0" do. 4 part 4.28X10 2. At 20C, 65 RI-I, the charge extinctive characteristic under an impressed voltage of 5000 V was measured with the following results:

Amount of addition Saturated Period of charge half decay Blank 2500 V Product of Example 8 1 part 1200 16 sec do. 2 part 1000 6 do. 3 part 900 2.3 do. 4 part 650 1.3

Control substance I pan 2000 23 do. 2 part 1500 19 do. 3 part 1200 13 do. 4 part 850 4.5

The above results testify to the superiority of the product of Example 8 to the surfactant of phosphate type in the anti-static effect for MMA resins.

B. Comparison between the reaction product of Example l and a conventional anti-static agent.

The anti-static effect for hardened vinyl chloride resin was compared with Catanao SN of the following structure:

-" ClHa 0 711350 ONI C3H Il ICgH4OH.N03

The results are as follows:

Fonnulations Vinyl chloride resin 100 100 parts Tributyl tin laurate 1 1 parts Catanao SN 1 0.7 pans Reaction product 0.3 parts of Example 1 Manufacturing process:

Extrusion method I40C, 5 minutes Heat stability test: Tests were made in a Geers oven at C 37 3 Test duration Specimen 20 min 40 min 60 min 80 min l min 120 min colorcolor colorcolorlight light Blank less less less less yellow yellow light light dark Formulation l black black black black yellow yellow brown color light light do. (2) brown red black less yellow yellow Anti-Static effect: At 20C, 55 RH the charge extinctive characteristic under impressed voltage of 5,000 V was measured The results are as follows Molding conditions:

with the following results: Pans l5 Formulation l) Polyethylene resin 100 Reaction product of Specimen Surface Saturated Period of mp 8 0.5

' i it If reslsuvlty charge a decay (Formulation ll) Polyethylene resin 100 Blank 669G010 2000 v Glyceryl monopalmitate 0.5

Formulation (l) 8.82Xl0 550 6 sec 20 Extrusion method: Using dies at 210C Anti-static effect:

As seen from the above results, the compound according to the present invention, when combined in use with an anti-static agent of cation type, can improve not only the anti-static effect but also the heat stability.

At C, 65 RH, the surface resistivity and frictional charge were measured with the following results (the value for blank polyethylene resin is 6.82 lO"Q):

C. Comparison between the reaction product of Example 14 and Tween 60 for anti-static effect on soft vi- 1. Immediately after molding nylchloride resln. The results are as follows:

Specimen Surface Frictional Formulations resistivity charge Molded film of (Formulation 1) formulation 1 2.88 l0fl l80V Vinyl chloride resin 100 parts DOP (dioctyl phthalate) parts do. ll 5.35 1() 250 Cadmium stearate soap 0.5 part Barium stearate soap 05 part Reaction roduct of Exam le 14 1 art p p p 2. After two months (Formulation ll) 40 Vinyl chloride resin 12% parts DOP dioct l hthalate) arts Cadmium sfeai ate soap 0.5 San Specimen q aq Fl'lclloflal Barium stearate soap 0.5 part l'eslsuvlty Charge Tween 60 1 part Molded film of Milling condition: formulation 1 3.32Xl0 fl 80 V Roll temperature 170 5C do. ll 1.87Xl0 130 Killing time 5 min Anti-static effect:

At 20C, 65 RH, the surface resistivity and friction 3. As adjusted to the condition of 20C, 65 RH for 24 hours after one hour of washing with water al charge were measured with the following results:

Specimen Surface Frictional Specimen resistivity charge Specimen Surface Frictional resistivity charge Molded m f formulation l 3.55XlO O 200 V Blank 2.36Xl0 Q 2000 V dc. ll 8137x10 2700 Molded product of formulation 1 2.30Xl0 250 do. ll 5.20xi0' 370 From the above results, it is clear that the compound according to the present invention, which possesses ex- The above results testify to the superiority of the compound according to the present invention to a conventional non-ionic surfactant of the ester of sorbitan type in its anti-static effect on soft vinyl chloride resin.

D. Comparison between the reaction product of Example 18 and glyceryl monopalmitate in the anti-static effect on polyethylene film.

cellent compatibility with a highly hydrophobic polyethylene resin, can give a stable anti-static effect.

Next, comparison in the decrease in surface tension, foaming power and wetting power was made between the surface-active organoboron compounds cited in the examples of this invention and the conventional nonionic surfactants, i.e., polyoxyethylene glycol fatty monoesters and a series of Tween surfactants. 

2. Surface-active organoboron compounds having the following structural formula:
 3. Surface-active organoboron compounds having the following structural formula:
 4. Surface-active organoboron compounds having the following structural formula:
 5. Surface-active organoboron compounds having the following structural formula:
 6. Surface-active organoboron compounds having the following structural formula:
 7. Surface-active organoboron compounds having the following structural formula
 8. Surface-active organoboron compound of claim 1, which is ( gamma -lauroylpoly oxyethylene glyceryl- Alpha , Beta , gamma ''-poly oxyethylene glyceryl- Alpha '', Beta '') boronium hydride having a total of 1-40 oxyethylene groups.
 9. Surface-active organoboron compound of claim 1, which is ( gamma -palmitoylpoly oxyethylene glyceryl- Alpha , Beta , gamma ''-poly oxyethylene glyceryl- Alpha '', Beta '') boronium hydride having a total of 1-40 oxyethylene groups.
 10. Surface-active organoboron compound of claim 1, which is ( gamma -stearoylpoly oxyethylene glyceryl- Alpha , Beta , gamma '' -poly oxyethylene glyceryl- Alpha '', Beta ''-) boronium hydride having a total of 1-40 oxyethylene groups.
 11. Surface-active organoboron coMpound of claim 1, which is ( Alpha -oleoylpoly oxyethylene glyceryl- Alpha , Beta , gamma ''-poly oxyethylene glyceryl- Alpha '', Beta ''- ) boronium hydride having a total of 1-40 oxyethylene groups.
 12. Surface-active organoboron compound of claim 1, which is bis ( Alpha -lauroylpoly oxyethylene glyceryl- Alpha , Beta -) boronium hydride having a total of 1-40 oxyethylene groups.
 13. Surface-active organoboron compound of claim 1, which is bis ( Alpha -linoleoylpoly oxyethylene glyceryl- Alpha , Beta -) boronium hydride having a total of 1-40 oxyethylene groups.
 14. Surface-active organoboron compound of claim 1, which is bis ( Alpha -stearoylpoly oxyethylene glyceryl- Alpha , Beta -) boronium hydride having a total of 1-40 oxyethylene groups.
 15. A process for production of the surface-active organoboron compounds, comprising first reacting one mol of boric acid or triesterborate of monohydric lower alcohol with two mols of polyhydric alcohol having vicinal hydroxyl radicals in such a manner that the total number of hydroxyl radicals, in the molecules of said polyhydric alcohol is 5 or more per boron atom in the molecule of boric acid or per boron atom in the molecule of lower alcohol triborate thereby producing a triester borate of said polyhydric alcohol; then adding 1-40 mols ethylene oxide for attachment to one mol of thus obtained triesterborate of said polyhydric alcohol retaining at least one free hydroxyl radical besides the hydroxyl radical forming semi-polar bond in the presence of non-protonic Lewis acid catalyst in such a manner that the average degree of polymerization of the polyoxyethylene radical in the molecule of the end product is 1-40; and then reacting at least one of the terminal hydroxyl radicals of the derived triester borate with a carboxylic acid having alkyl groups having 7 to 31 carbon atoms or a lower alcohol ester of said carboxylic acid or an acylhalide of said carboxylic acid.
 16. The process for the production of the surface-active organoboron compounds of claim 15, whereby 24 mols of ethylene oxide is subjected to the addition reaction using 3% by weight boron trifluoride as said catalyst, to one mol of a triester borate obtained from one mol of boric acid and two mols of glycerine; and then a carboxylic acid ester is derived through reaction with one to two mol of lauric acid, stearic acid, oleic acid or linoleic acid.
 17. The process for production of the surface-active organoboron compounds in claim 15 whereby 24 mols of ethylene oxide is subjected to the addition reaction using 3% by weight boron trifluoride as catalyst, to one mol of a triester borate obtained from one mol of boric acid and two mols of glycerine; and then a carboxylic acid ester is derived through reaction with one mol of palmitic acid chloride or stearic acid chloride. 